Carbon‐Stabilized High‐Capacity Ferroferric Oxide Nanorod Array for Flexible Solid‐State Alkaline Battery–Supercapacitor Hybrid Device with High Environmental Suitability

Iron oxides are promising to be utilized in rechargeable alkaline battery with high capacity upon complete redox reaction (Fe 3+ Fe 0 ). However, their practical application has been hampered by the poor structural stability during cycling, presenting a challenge that is particularly huge when binder‐free electrode is employed. This paper proposes a “carbon shell‐protection” solution and reports on a ferroferric oxide–carbon (Fe 3 O 4 –C) binder‐free nanorod array anode exhibiting much improved cyclic stability (from only hundreds of times to >5000 times), excellent rate performance, and a high capacity of ≈7776.36 C cm −3 (≈0.4278 C cm −2 ; 247.5 mAh g −1 , 71.4% of the theoretical value) in alkaline electrolyte. Furthermore, by pairing with a capacitive carbon nanotubes (CNTs) film cathode, a unique flexible solid‐state rechargeable alkaline battery‐supercapacitor hybrid device (≈360 μm thickness) is assembled. It delivers high energy and power densities (1.56 mWh cm −3 ; 0.48 W cm −3 /≈4.8 s charging), surpassing many recently reported flexible supercapacitors. The highest energy density value even approaches that of Li thin‐film batteries and is about several times that of the commercial 5.5 V/100 mF supercapacitor. In particular, the hybrid device still maintains good electrochemical attributes in cases of substantially bending, high mechanical pressure, and elevated temperature (up to 80 °C), demonstrating high environmental suitability.